US11512251B2 - Rare-earth halide scintillating material and application thereof - Google Patents

Rare-earth halide scintillating material and application thereof Download PDF

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US11512251B2
US11512251B2 US16/620,850 US201816620850A US11512251B2 US 11512251 B2 US11512251 B2 US 11512251B2 US 201816620850 A US201816620850 A US 201816620850A US 11512251 B2 US11512251 B2 US 11512251B2
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rare
scintillating material
earth
earth halide
halide
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US20200318005A1 (en
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Jinqiu YU
Chengpeng DIAO
Hao Wu
Lei Cui
Huaqiang He
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Grirem Advanced Materials Co Ltd
Beijing General Research Institute for Non Ferrous Metals
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Grirem Advanced Materials Co Ltd
Beijing General Research Institute for Non Ferrous Metals
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
    • C09K11/7719—Halogenides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/253—Halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/253—Halides
    • C01F17/271—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7772—Halogenides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/12—Halides
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/16—Measuring radiation intensity
    • G01T1/20—Measuring radiation intensity with scintillation detectors
    • G01T1/202—Measuring radiation intensity with scintillation detectors the detector being a crystal
    • G01T1/2023—Selection of materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B47/00—Survey of boreholes or wells
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B49/00—Testing the nature of borehole walls; Formation testing; Methods or apparatus for obtaining samples of soil or well fluids, specially adapted to earth drilling or wells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/29—Measurement performed on radiation beams, e.g. position or section of the beam; Measurement of spatial distribution of radiation
    • G01T1/2914—Measurement of spatial distribution of radiation
    • G01T1/2985—In depth localisation, e.g. using positron emitters; Tomographic imaging (longitudinal and transverse section imaging; apparatus for radiation diagnosis sequentially in different planes, steroscopic radiation diagnosis)
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/36—Measuring spectral distribution of X-rays or of nuclear radiation spectrometry
    • G01T1/362—Measuring spectral distribution of X-rays or of nuclear radiation spectrometry with scintillation detectors

Definitions

  • the present invention relates to the field of inorganic scintillating materials, and more particularly, to a rare-earth halide scintillating material and application thereof.
  • a scintillating material can be configured to detect such high-energy rays as ⁇ -rays, ⁇ -rays, X-rays, and such high-energy particles as neutrons, and is extensively used in the fields of nuclear medicine, high-energy physics, security inspection, oil logging, etc.
  • the scintillating material is usually applied in the form of single crystals, and in some cases may also be in ceramic or other forms.
  • the demands on the performance of the scintillating material are different.
  • the scintillating material it is desirable for the scintillating material to have a light yield as high as possible, a decay time as short as possible, and an energy resolution as high possible.
  • nuclear medicine imaging devices as a positron emission tomography (PET)
  • PET positron emission tomography
  • a LaBr 3 :Ce crystal disclosed by E. V. D. van Loef et al. in 2001 has a very high light output (>60,000 ph/MeV), a very short decay time ( ⁇ 30 ns) and a very high energy resolution (about 3%@662 keV) and thus is a scintillating material with extremely excellent performance.
  • Other rare-earth halide scintillating crystals that have been disclosed include: CeBr 3 , LaCl 3 :Ce, LuI 3 :Ce, YI 3 :Ce and GdI 3 :Ce, which also have excellent scintillation properties.
  • rare-earth halide scintillating crystals are all stoichiometric compounds, and rare-earth ions in these compounds are in stable +3 valence.
  • Doping with an alkaline earth metal ion can further improve the energy resolution and the energy response linearity of the LaBr 3 :Ce crystal.
  • due to differences in radius and valence state between the alkaline earth metal ion and the rare-earth ion such doping is liable to cause crystal growth defects and is relatively limited in doping concentration.
  • Co-doping a halogen ion and the alkaline earth metal ion can effectively solve this problem, increase the doping concentration of the alkaline earth metal ion and reduce the crystal growth defects.
  • this solution also has its shortcomings. That is, the compositions are relatively complicated, and the consistency of the scintillation property of the crystal is poor due to uneven distribution of the different ions.
  • the rare-earth ion and alkaline earth metal ion in the doped LaBr3:Ce crystal are respectively in stable +3 valence and +2 valence.
  • the doped LaBr3:Ce crystal is also a stoichiometric compound. Therefore, a heretofore unaddressed need exists in the art to address the aforementioned deficiencies and inadequacies.
  • a main objective of the present invention is to improve the performance of a conventional rare-earth halide scintillating material by providing a rare-earth halide scintillating material and application thereof.
  • a rare-earth halide scintillating material having a chemical formula of RE a Ce b X 3 , wherein RE is a rare-earth element La, Gd, Lu or Y, X is one or two of halogens Cl, Br and I, 0 ⁇ a ⁇ 1.1, 0.01 ⁇ b ⁇ 11.1, and 1.0001 ⁇ a+b ⁇ 1.2.
  • RE is La
  • X is Br
  • RE is La
  • X is Cl
  • RE is Gd, Lu or Y, and X is I.
  • the scintillating material is a single crystal.
  • the rare-earth halide scintillating material is obtained by the Bridgeman-Stockbarge method.
  • a scintillation detector including a scintillating material which is any of the rare-earth halide scintillating materials described above.
  • a PET a gamma spectrometer, an oil logging instrument or a lithology scanning imager including the above-mentioned scintillation detector.
  • a +2 valent rare-earth halide for example, LaBr 2
  • a heterogeneous alkaline earth metal halide for example, SrBr 2
  • the rare-earth halide scintillating material is relatively short of a halogen ion.
  • the apparent valence state of a rare-earth ion is between +2 and +3.
  • the rare-earth halide scintillating material belongs to non-stoichiometric compounds, but still retains a crystal structure of an original stoichiometric compound, and has more excellent energy resolution and energy response linearity than the stoichiometric compound.
  • a rare-earth halide scintillating material having the chemical formula of RE a Ce b X 3 , wherein RE is a rare-earth element La, Gd, Lu or Y, X is one or two of halogens Cl, Br and I, 0 ⁇ a ⁇ 1.1, 0.01 ⁇ b ⁇ 1.1, and 1.0001 ⁇ a+b ⁇ 0.2.
  • the rare-earth halide scintillating material provided by the present invention by taking a +2 valent rare-earth halide (for example, LaBr 2 ) having the same composition as a dopant to replace a heterogeneous alkaline earth metal halide (for example, SrBr 2 ) in the prior art for doping, not only can the same doping effect be achieved but also the problems of uneven segregation, etc. caused by introduction of a heterogeneous alkaline earth metal ion can be effectively avoided.
  • the rare-earth halide scintillating material is relatively short of a halogen ion. The apparent valence state of a rare-earth ion is between +2 and +3.
  • the rare-earth halide scintillating material belongs to non-stoichiometric compounds, but still retains a crystal structure of an original stoichiometric compound, and has more excellent energy resolution and energy response linearity than the stoichiometric compound.
  • RE and X are combined in any of the following ways: La and Br, La and Cl, Gd and I, Lu and I, and Y and I.
  • Rare-earth halides adopting the above combinations have more excellent performance than rare-earth halides adopting other combinations. Scintillating materials formed by the same rare-earth element and different halide ions have different scintillation properties. For example, in Ce 3+ -activated lanthanum halide, LaBr 3 has a very high light yield, LaCl 3 also has a relatively higher light yield which is obviously lower than that of LaBr 3 , and LaI 3 almost does not emit light at room temperature.
  • the proportion of a rare-earth ion to a halide ion in a non-stoichiometric compound is only limited to a relatively narrower range.
  • the value range of the rare-earth ion is 1.0001 ⁇ a+b ⁇ 1.2, preferably, 1.0001 ⁇ a+b ⁇ 1.1.
  • An over high proportion of the rare-earth ion will cause a series of problems including decrease of the crystal light yield, increase of the crystal growth defect, etc., which may be related to the increase of halide ion vacancies, the change of a crystal energy band structure and phase segregation.
  • the proportion of the rare-earth ion in the rare-earth halide scintillating material is within the above preferred range.
  • the rare-earth halide scintillating material is in the form of powder, ceramics or single crystals, and is preferably applied in the form of single crystals obtained by the Bridgeman-Stockbarge method.
  • the present invention further relates to a scintillation detector including the rare-earth halide scintillating material, as well as a PET, a gamma spectrometer, an oil logging instrument or a lithology scanning imager including the scintillation detector.
  • a scintillation detector including the rare-earth halide scintillating material, as well as a PET, a gamma spectrometer, an oil logging instrument or a lithology scanning imager including the scintillation detector.
  • Relevant devices adopting the rare-earth halide scintillating material provided by the present invention are relatively higher in consistency of crystal scintillation properties.
  • the rare-earth halide scintillating material provided by the present invention is a non-stoichiometric compound. That is, the apparent valence state of the rare-earth ion is not generally +3, but between +2 and +3.
  • the consistency of the scintillation property of the rare-earth halide scintillating material is improved by adjusting the proportion of the rare-earth ion to the halide ion.
  • the present invention initially studies the doping modification solution of LaBr 3 :Ce to solve the problems of too complicated compositions, difficult crystal growth and poor consistency of the scintillation property, caused by co-doping of the halide ion and an alkaline earth metal ion in a conventional doping solution.
  • the function mechanism that the alkaline earth metal ion is doped to improve the scintillation property of a LaBr 3 :Ce crystal is not yet very clear. It is generally believed that this function mechanism is relevant to a valence transition of some Ce 3+ to Ce 4+ in the crystal arising from the doping of a +2 valent alkaline ion.
  • the inventor proposes that by taking a +2 valent rare-earth halide (for example. LaBr 2 ) having the same composition as a dopant to replace a heterogeneous alkaline earth metal halide (for example, SrBr 2 ) in the prior art for doping, not only can the same doping effect be theoretically achieved but also the problems of uneven segregation, etc. caused by introduction of a foreign ion can be effectively avoided.
  • a rare-earth halide obtained in this way is relatively short of a halogen ion.
  • the apparent valence state of a rare-earth ion is between +2 and +3.
  • the rare-earth halide is a non-stoichiometric compound.
  • the +2 valent rare-earth halide with the unstable valence state for example, LaBr 2
  • another equivalent solution is adopted in the present invention for replacement. That is, a small amount of a rare-earth metal (for example, La) is added into the stable stoichiometric rare-earth halide (for example, LaBr 3 ) and high-temperature melting is performed to obtain a target non-stoichiometric rare-earth halide having a uniform composition.
  • a rare-earth metal for example, La
  • LaBr 3 stable stoichiometric rare-earth halide
  • high-temperature melting is performed to obtain a target non-stoichiometric rare-earth halide having a uniform composition.
  • the stoichiometric rare-earth halide and the rare-earth metal, of which the production methods are mature, are readily available on the market, the alternative solution is relatively lower in cost and is operable.
  • a non-stoichiometric lanthanum bromide crystal obtained in the present invention has an extremely excellent scintillation property, and its comprehensive performance is obviously superior to that of a conventional undoped lanthanum bromide crystal, and is superior to those of alkaline-earth-doped and alkaline earth and halide ion co-doped lanthanum bromide crystals, wherein the superiority is embodied in that the light yield of the crystal is increased to some extent, the decay time is shortened significantly and the energy resolution is improved to some extent. This may be relevant to a halide ion vacancy in the non-stoichiometric crystal.
  • the defect level contributed by the halogen ion vacancy may reduce the band gap of the crystal, resulting in an increase in the light yield of the crystal.
  • the halogen ion vacancy makes it easier to form Ce 4+ in the crystal, thereby shortening the luminescence decay time.
  • the non-stoichiometric lanthanum bromide crystal is free from impurity segregation and is greatly improved in homogeneity.
  • the growth process of the non-stoichiometric lanthanum bromide crystal is free from such crystal defects as an inclusion and a crack due to impurity enrichment.
  • the yield of the crystal is improved significantly.
  • the production cost of the crystal is effectively lowered.
  • the light yield and the energy resolution are obtained through multichannel spectrum detection based on a 137 Cs radioactive source.
  • the decay time is detected by the X-ray fluorescence spectrometry.
  • anhydrous LaBr 3 (the purity is 99.99%, that is, the mass content of LaBr 3 is 99.99%, and the following purity means the same) and 6.33 g of anhydrous CeBr 3 (with the purity of 99.99%) are accurately weighed in a glove box under atmosphere protection, and mixed uniformly.
  • the obtained mixture is charged into a quartz crucible with the diameter of 25 mm.
  • the quartz crucible is taken out of the glove box and quickly connected to a vacuum system to be vacuumized. When the vacuum degree is 1*10 ⁇ 3 Pa, an opening of the quartz crucible is sealed by fusing.
  • the quartz crucible is placed in a Bridgeman crystal oven for single-crystal growth.
  • the temperature of a high-temperature area is 850° C.
  • the temperature of a low-temperature area is 700° C.
  • a gradient area has a temperature gradient about 10° C./cm.
  • the crucible descends at a rate of 0.5 mm/h to 2 mm/h.
  • the total growth time is about 15 days.
  • the obtained crystal is transparent and colorless and is about 5 cm in length.
  • the crystal is cut and processed in the glove box into a cylindrical sample of ⁇ 25 mm*25 mm. After that, tests of the light yield, the decay time and the energy resolution are performed.
  • Embodiments 2 to 13 are the same as those of Embodiment 1, except for raw material ratios.
  • the non-stoichiometric crystal provided by the present invention has extremely excellent scintillation property and shows a relatively more remarkable performance advantage. While the high material performance is guaranteed, the material composition is remarkably simplified, which contributes to obtaining of the high-quality scintillating crystal with favorable consistency.
  • the above embodiments achieve the following technical effect: by adjusting the proportion of the rare-earth ion to the halide ion, a conventional stoichiometric rare-earth halide scintillating material is converted into the non-stoichiometric compound, such that the scintillation property and the growth consistency of the rare-earth halide scintillating material are improved.

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CN201711446351.5 2017-12-27
CN201711446351.5A CN109988577B (zh) 2017-12-27 2017-12-27 稀土卤化物闪烁材料及其应用
PCT/CN2018/110183 WO2019128388A1 (zh) 2017-12-27 2018-10-15 稀土卤化物闪烁材料及其应用

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CN109988577B (zh) * 2017-12-27 2020-12-25 有研稀土新材料股份有限公司 稀土卤化物闪烁材料及其应用
CN110938868B (zh) * 2019-11-01 2022-02-22 有研稀土新材料股份有限公司 稀土卤化物闪烁材料
CN110982527B (zh) * 2019-11-01 2021-12-14 有研稀土新材料股份有限公司 稀土卤化物闪烁材料

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